Sym-tetrafluorodichloroisopropyl acrylate compounds and polymers thereof



United States Patent 3,177 187 SYM TETRAFLUOROl)ICHLOROISOPROPYL ACRYLATE (ZOMPOUNDS AND PGLYMERfi THEREOF Jerome Hollander and Cyril Woolf, Morristown, N.J., assignors to Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Oct. 28, 1963, Ser. No. 319,590

I 14 Claims. ((Jl. 260-895) This invention relates to new fiuorochlorinated acrylic compounds, and more particularly, to new sym-tetrafiuorodichloroisopropyl acrylate and sym-tetrafiuorodichloroisopropyl methacrylate, their polymers and processes for their preparation.

Polymers prepared from the monesters of acrylic acid and its derivatives have been long recognized as thermoplastic materials whose utility is both wide and varied. Numerous as these applications may be, however, acrylic polymers in general have been limited to those environments which are exposed to limited thermal conditions since they inherently possess a degree of thermal instability. Moreover, these acrylic materials have frequently been found to support combustion which of course, eliminates their utility from those industrial applications wherein combustible materials may not, of

T necessity, be employed.

V propyl alcohol, although a secondary alcohol comprised of less than carbon atoms when reacted with acrylic acid or methacrylic acid or derivatives thereof produces an intermediate fluorochlorinated monomer which, when converted to its corresponding polymer, possesses outstanding thermal and dimensional stability. Moreover, these fluorochlorinated acrylic polymers derived from sym-tetrafiuorodichloroisopropyl alcohol, when utilized as fiber impregnators, exhibit outstanding and unexpected oleophobi'c and hydrophobic properties as 'is described in our co-pending U.S; application Serial No. 319,514 filed of even date. In addition, the fluorochlorinated acrylic fiber impregnators exhibit remarkable penetrating and wetting ability and the fiber treated thereby exhibits excellent hand or feel' qualities.

Our co-pending US. application Serial No. 319,546, filed of even date, discloses and claims sym-hexafluoroisopropyl acrylate and methacrylate compounds, homopolymers derived therefrom and process for their preparation.

Accordingly, it is a principal object of the present invention to provide new sym-tetrafiuorodichloroisopropyl acrylate and sym-tetrafluorodichloroisopropyl methacrylate.

It is a further object of the present invention to provide new fluorochlorinated acrylic polymers derived from symtetrafluorodichloroisopropyl acrylate and sym-tetrafiuorodichloroisopropyl methacrylate.

It is still a further object to provide processes for preparing sym-tetrafiuorodichloroisopropyl acrylate and sym-tetrafluorodichloroisopropyl methacrylate and their corresponding acrylic polymers. Other objects and advantages will become apparent from the following description.

In accordance with the present invention, new fluorochlorinated acrylic polymers may be prepared by polympreferably 0.5 to 1.5 parts, per part sym-tetrafiuorodi- 'ice erizing a fluorochlorinated acrylic monomer of the formula isopropyl acetone by hydrogenation.

The fiuorochlorinated acrylic monomers of the present invention may be prepared by reacting sym-tetrafluorodichloroisopropyl alcohol with an acrylic compound of the formula wherein X is a member selected from the group consisting of chlorine, hydroxyl and methoxy and R is a member selected from the group consisting of hydrogen and methyl. It is to be understood of course that the acrylic reactant may also be employed in the form of its acid anhydride. Thegeneral formula for such acrylic. acid anhydride reactants is:

1r,o =o--o /o HQC C O wherein R is hydrogen or methyl. In preferred operation,

acrylyl chloride or methacrylyl chloride is employed.

The molar ratio of the reactants is not critical and from about 0.1 mol to about 10 mols sym-tetrafluorodichloroisopropyl alcohol per mol acrylic reactant maybe employed to secure the desired reaction product. It is preferred, however, in order to secure highest yields, that a substantially stoichiometric molar ratio of about 1:1 be

employed. I

A suitable solvent, if desired, may be employed to serve as. a dilutent and to facilitate reaction at elevated temperatures. Generally speaking, any solvent may be employed provided it is inert under the conditions of'reaction and a solvent for the reactants. Illustrative of such solvents are pyridine, quinoline, dimethyl aniline, trifluoroacetic acid, decalin and 1,1,2-trifiuoro-1,2,2-trichloroethane.

In order to minimize reaction time a suitable esterification' catalyst such as pyridine, quinoline, trifiuoroacetic acid, ptoluene 'sulfonic acid, phosphoric acid and sul" furic acid, may be employed. The amount. of catalyst is not critical and may range from about 1.0 to 200%,

preferably 5% to 50%, by weight based on the amount of syrn-tetrafluorodichloroisopropyl:alcohol charged.-

In preferred operation, however, pyridine is employed since it acts as both a solvent and a catalyst. Generally, theamo-ut, of pyridine employed is about 0.10 to 2.0 parts,

Patented Apr. 6, 1965 with ether.

- but soluble in ether and acetone.

fluorodichloroisopropyl acrylate was heated at 200 C. for a period of 24 hours after which it was found to ex-:

chloroisopropyl alcohol charged. The reactiontemperature may vary over a wide range, i.e. from about room temperature up to the boiling point of the reaction mixture. In preferred operation, a temperature selected from the range of from about room temperature to 100 C.

v is utilized with a mild agitation of the reaction mixture:

Although acrylyl or methacrylylchlorideis used in 1 preferred operation, the acid or anhydride form of the acrylic reactant may be successfully employed to effect esterification in the presence of a dehydrating and esterification catalyst suchas trifiuoroacetic acid, sulfuric acid and p-toluene sulfonic acid under the same reaction conditions recited herein.

Recovery and purification of the resulting sym-tetrafluorodichloroisopropyl acrylate or sym-tetrafluorodichloroisopropyl methacrylate may be effected by employing conventional procedures. For example, the entire reaction'rnixture may be'added to a nonsolventsuch as water followed by extraction with a solvent such as ether followed by evaporating off of the solvent. Also,distillation of excess reactants and solvent may be employed. Purification procedure may comprise neutralizing acid byproduct With a dilute aqueous alkaline solution, watera washing followed by oven-drying.- V

Sym-tetrafluorodichloroisopropyl acrylate and sym-1 tetrafluorodichloroisopropyl methacrylate are readily polymerized, even in the absence of a polymerization catalyst by simply heating at moderate temperatures, i.e. room temperature to about 125 C. Since. these fluorochloe.

To a cooled vessel containing.28.0 parts of sym-tetrafluorodichloroisopropyl alcohol was added 11.8parts of acrylyl chloride in a dropwise manner with constant stirring. The resulting reaction mixture was. stirred for 0.5 hour at' room temperature and then for 5 hours at reflux temperature (140 C-.). The reaction mixture containing the resulting sym-tetrafluorodichloroisopropyl acrylate was poured into cold water :followed by extraction aqueous solution of sodium carbonate to neutralize any trace amount of by-product hydrogen chloride. ether was removed by distillation whereupon crude symtetrafiuorodichloroisopropyl acrylate was. obtained as a from the. aqueous phase and a dilute aqueoussolution of The ether extracts were washed wi-th'a dilute The I yellow liquid. Purification was effected by distillation to'yieldv 24.3, parts of syrn tetrafiuorodichloroisopropyl acrylate as a clear, colorless liquid. Elemental analysis showed 48.2% fluorine and 2.48% hydrogen'which is in excellent agreement' with the theoreticalvalues of 48.1% fluorine and 2.55% hydrogen.

f 6.4 parts of sym-tetrafluorodichloroisopropyl 'acrylate so prepared were then placed in an evacuated, sealed tube and irradiated with ultra-violet light for 19 hours. The resulting poly-sym-tetrafluorodichloroisopropyl acrylate was a clear, "water-white solid which was insoluble in carbon tetrachloride, chloroform and carbon disulfide hibit only a slight amber discoloration.

v 8 Example 2 The poly-sym-tetra- 4.. fluorodichloroisopropyl alcohol was added 70.9 parts of methacrylyl chloride in a dropwise manner with constant stirring. The resulting reaction mixture was heated at reflux temperature for a period of 10 hours. The reaction mixture containing sym tetrafluorodichloroisopropyl methacrylatewaspouredinto cold water followed by extraction with ether. The, ether extracts were segregated sodium car'bonatewas added to neutralize any trace amount of hydrogen chloride by-product. Any trace of water was then removed by the addition of anhydrous sodium sulfate. The ether was removed by distillation and crude sym-tetrafluorodichloroisopropyl methacrylate was isolated as a yellow liquid. Purification by distillation yielded 103 parts of sym-tetrafiuorodichloroisopropyl methacrylate as a. clear colorlessqliquid. Elemental analysis showed 28.3% fluorine which is in accordance with the theoretical value of 27.5%.

17.5 parts of sym-tetrafluorodichloroisopropyl methacrylate so prepared and 0.02 part of benzoyl peroxide were charged to an evacuated,.:sealedglass tube. The evacuated tube containing this reaction'rnixture was kept at 50 C. for a period of 5 days. 16.6 parts of polysyrn-tetrafiuorodichloroisopropyl methacrylate as a soft, rubbery solid were obtained and dissolved in acetone. Recovery of poly-sym-tetrafluorodichloroisopropyl methacrylate was effected by the addition of methanol, a nonsolvent, to the acetone solution,-whereupon the polymer precipitated out as a finely divided .white powder. The

polymer was then oven dried at C. undera pressurev of 25 pounds/inch for a period of 24 hours. 8.1 parts of poly-sym-tetrafiuorodichloroisopropyl methacrylate as a White powder were obtained.

Example 3 e Example 4 17.5 parts of sym-tetrafiuorodichloroisopropyl meth acrylate prepared by the procedure set forth inExample 2 and 0.02 part of benzoyl peroxide were placed in an evacuated sealed tube followed by irradiation with ultraviolet light in an icewater bath cooled .to 0 C. for a period of 25 hours. Irradiation was then continued at room temperature forv an additional periodof 17 hours. The resulting poly sym's tetrafiuorodichloroisopropyl methacrylate was recovered as a clear, water-white, hard solid. This solid polymer was then dissolved in acetone andrecovered by the addition of the acetone solution to 8.7 parts: of polysym-tetramethanol, a nonsolvent. fluorodichloroisopropyl methacrylate was recovered as a finely dividedwhite powder followed bydrying under vacuum for 24 hours.

- This invention may be embodied in other'forms or carried out in other Ways without departing from the spirit or essential characteristics thereof. The present. embodiment is, therefore, to be considered in all respects as. illustrative and not restrictive, the scope of the invention being indicated by the appended claims.

Weclaim: i 1. Fluorochlorinated acrylic compounds having the formula wherein 'R is amember selected from the group consistingof hydrogen and methyL: i e

2. Sym-tetrafluorodichloroisopropyl acrylate. 3. Sym-tetrafiuorodichloroisopropyl methacrylate. 4. A fiuorochlorinated acrylic homopolymer derived from a monomer having a formula R 0 C1 n,o=o-o r-cr 0* I H F-(|3-F 01 wherein R is a member selected from the group consisting of hydrogen and methyl.

5. A homopolymer in accordance with claim 4 wherein the monomer is sym-tetrafluorodichloroisopropyl acrylate.

6. A homopolymer in accordance with claim 4 wherein the monomer is sym-tetrafiuorodichloroisopropyl methacrylate.

7. A process for the preparation of a fluorochlorinated acrylic compound having the formula ing of chlorine, hydroxyl and methoxy and R is a member selected from the group consisting of hydrogen and methyl in a molar ratio of from about 0.1 to 10 mols sym-tetrafluorodichloroisopropyl alcohol per mol acrylic compound at a temperature from about room temperature to the boiling point of the reaction mixture and recovering the resulting fluorochlorinated acrylic compound.

8. A process in accordance with claim 7 wherein the acrylic compound is employed in the form of its acid anhydride. I

9. A process in accordance with claim 7 wherein the reaction is conducted in the presence of an inert solvent.

10. A process in accordance with claim 7 wherein an esterification catalyst is employed.

11. A process for the preparation of chlorofiuorinated acrylic polymers which comprises homopolymerizing by heating a monomer of the formula 0- -11 F E F wherein R is a member selected from the group consist ing of hydrogen and methyl.

12. A process in accordance with claim 10 wherein a polymerization catalyst is employed.

13. A process in accordance with claim 11 wherein the polymerization catalyst is an organic peroxide.

14. A process in accordance with claim 10 wherein the polymerization is carried out by actinic radiation.

No references cited.

JOSEPH L. SCHOFER, Primary Examiner.

DONALD E. CZAJA, Examiner. 

11. A PROCESS FOR THE PREPARATION OF CHLOROFLUORINATED ACRYLIC POLYMERS WHICH COMPRISES HOMOPOLYMERIZING BY HEATING A MONOMER OF THE FORMULA 